CN104262391B - A kind of environment friendly clean producing method of high-purity glufosinate-ammonium - Google Patents
A kind of environment friendly clean producing method of high-purity glufosinate-ammonium Download PDFInfo
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Abstract
The invention discloses the environment friendly clean producing method of a kind of high-purity glufosinate-ammonium, comprise the following steps: 1) by methyl phosphinate compound and acrylic aldehyde generation additive reaction；2) methyl phosphinate derivatives quasi-compound is generated methyl phosphinate cyanohydrin compound with cyanide；3) methyl phosphinate cyanohydrin compound is reacted with ammonia；4) by amino nitrile derivative compound basic hydrolysis；5) phosphine oxamate two saline solution carrying out bipolar membrane electrodialysis process, salt room controls pH=2.5～3.5 and obtains the mixed solution of phosphine oxamate and phosphine oxamate one salt；6) crystallisation by cooling after being concentrated by the mixed solution of phosphine oxamate with phosphine oxamate one salt, crystalline mother solution circulation carries out bipolar membrane electrodialysis process；7) phosphine oxamate is reacted with ammonia, prepare glufosinate-ammonium.Present invention, avoiding substantial amounts of abraum salt waste water to produce, and the glufosinate-ammonium purity obtained is high, yield is high, and current utilization rate is high, energy-saving and cost-reducing, reduce production cost.
Description
Technical field
The present invention relates to the production technical field of glufosinate-ammonium, the environmental protection being specifically related to a kind of high-purity glufosinate-ammonium is clear
Clean production method.
Background technology
Glufosinate-ammonium is a kind of high-efficiency low-toxicity non-selective (property killed) contact killing type with partial internal absorbance effect
Organic phosphates herbicide, soluble in water, insoluble in organic solvent.Glufosinate-ammonium toxicity is low, safer,
Being prone to degraded in soil, to crop safety, drift about little, herbicidal spectrum is wide, and activity is high, and consumption is few, environment pressure
Power is little.In recent years, glufosinate-ammonium is increasingly subject to people's attention, and production technology mainly has bioanalysis and chemistry
Method, wherein chemical method is prone to industrialized production.Synthetic method currently mainly has A Buzuofu synthetic method, height
Pressure catalysis synthesis process, low temperature controlled syntheses method, drop cloth riel-diethyl malonate, Si Chuike-Ze Lin
Si Jifa, chiral synthon method, A Buzuofu-Michael's synthetic method etc..
But, with the generation of inorganic salt during chemical synthesis, such as sodium sulfate, sodium chloride, chlorine
Change ammonium, ammonium sulfate etc., owing to glufosinate-ammonium and the inorganic salt dissolubility in water is the biggest, use conventional side
Method is difficult to separate, and general employing adds organic solvent such as methanol, ethanol etc. miscible with water, utilizes glufosinate-ammonium
Separate with the difference of inorganic salt solvent in alcohol, but the method consumes substantial amounts of solvent, and also
Produce the inorganic salt of substantial amounts of low value." the grass that the 6th phase of volume 30 in June, 2007 " Hebei chemical industry " delivers
The ion exchange resin purification technique of ammonium phosphine " method that have employed ion exchange resin in a literary composition separates grass ammonium
Inorganic salt in phosphine solution, can reach the highest purity, but the resin price that the method uses is high,
Operation is complicated, yield only has less than 80%, and glufosinate-ammonium loss is serious.Patent CN103483377A discloses
A kind of utilize storng-acid cation exchange resin to separate the inorganic salt in glufosinate-ammonium solution, but face equally
The problems referred to above.Inorganic salt owing to producing in glufosinate-ammonium building-up process does not has good technology to separate, and makes
The industrialized production obtaining glufosinate-ammonium is difficult to promote.
For the preparation method of glufosinate-ammonium, more and comparative maturity the technique of report is mainly sub-by methyl at present
React with Cyanogran. again after phosphonic acid ester and acrolein reaction and obtain cyanamide compound, obtain through acid hydrolysis
Glufosinate-ammonium (patent US6359162 or JP7900405), its process chart is as shown in Figure 1.This technique
Route is short, reaction condition is gentle, yield is higher, and shortcoming is with Cyanogran. as cyanating reagent, produces big
The abraum salt sodium chloride of amount, produces environmental protection pressure, and with in acid hydrolysis, the ammonium chloride of generation is rear
Removing more difficult during phase recrystallization refined product, technique is loaded down with trivial details, especially subsequent product glufosinate-ammonium and ammonium chloride
Isolated and purified, both water solublity is preferable, needs water is carried out substantial amounts of concentration, therefore, causes
The purity of glufosinate-ammonium product is the highest, and the ammonium chloride of by-product contains glufosinate-ammonium, and can not sell, and produces a large amount of
Waste residue.
Visible, no matter which kind of route is glufosinate-ammonium use prepare, and the most common method is ammonia or ammonia to be added
Enter in the mixed liquor of phosphine oxamate and inorganic salt and be neutralized, thus obtain the mixture of glufosinate-ammonium and inorganic salt,
Utilize glufosinate-ammonium and inorganic salt different solubility in water, thus reach the purpose of Crystallization Separation purification.But
It is, such isolation and purification method that the glufosinate-ammonium purity obtained is the highest, containing grass ammonium in the inorganic salt of by-product
Phosphine, produces substantial amounts of waste water and waste residue, and the yield of glufosinate-ammonium is the highest.
Summary of the invention
In view of this, it is an object of the invention to provide the environment friendly clean producing method of a kind of high-purity glufosinate-ammonium,
It is avoided that the generation of by-product inorganic salt, and glufosinate-ammonium product purity is high, yield is high, energy-saving and cost-reducing, reduce
Production cost.
For reaching above-mentioned purpose, the present invention provides following technical scheme:
The environment friendly clean producing method of the high-purity glufosinate-ammonium of the present invention, comprises the following steps:
1) methyl phosphinate compound I and acrylic aldehyde generation additive reaction are generated methyl phosphinate to derive
Species compounds Ⅳ；
2) by step 1) to generate methyl sub-for the methyl phosphinate derivatives quasi-compound that obtains IV and cyanide
Phosphonate ester cyanohydrin compound V；
3) by step 2) the methyl phosphinate cyanohydrin compound V that obtains reacts with ammonia, obtains amino nitrile and spread out
Raw compounds VI；
4) by step 3) amino nitrile derivative compound VI basic hydrolysis that obtains, obtain phosphine oxamate two saline solution；
5) with step 4) phosphine oxamate two saline solution that obtains as raw material, enter bipolar membrane electrodialysis system and enter
Row bipolar membrane electrodialysis processes, and it is molten with the mixing of phosphine oxamate one salt that salt room control pH=2.5～3.5 obtains phosphine oxamate
Liquid, alkali room obtains aqueous slkali；
6) by step 5) mixed solution of the phosphine oxamate that obtains and phosphine oxamate one salt concentrate after crystallisation by cooling,
To phosphine oxamate and crystalline mother solution, crystalline mother solution is recycled to step 5) enter bipolar membrane electrodialysis system carry out bipolar
EDBM processes；
7) by step 6) phosphine oxamate that obtains reacts with ammonia, prepares glufosinate-ammonium.
Further, described step 1) in, methyl phosphinate compound I can be methyl methylphosphinate,
Methyl phosphonous acid ethyl ester, methyl phosphonous acid isopropyl ester etc., preferably methyl phosphinate compound I are that methyl is sub-
Methyl-phosphonate, methyl methylphosphinate is at acetic anhydride, DMF with the additive reaction of acrylic aldehyde
With carry out in the presence of methanol, methyl methylphosphinate is 1:1.0～1.05 with the molar ratio of acrylic aldehyde,
Acetic anhydride is 1:1.0～1.05 with the mol ratio of acrylic aldehyde, and the consumption of DMF is methyl phosphonous acid
The 0.1%～5% of methyl ester quality, reaction temperature is 0～50 DEG C, and the response time is 2～5 hours.
Further, described step 2) in, cyanide can be Cyanogran., potassium cyanide, Cyanogas (Am. Cyanamid)., hydrocyanic acid
Deng, preferably cyanide is hydrocyanic acid, and hydrocyanic acid is rubbed with feeding intake of methyl phosphinate derivatives quasi-compound IV
Your ratio is 1.0～1.1:1, and pH during cyaniding is 6～7, and the temperature of cyanogenation controls at 25～40 DEG C, cyanogen
The change response time is 3～4 hours.
Further, described step 3) in, ammonia is ammonia or ammonia, methyl phosphinate cyanohydrin compound V
Being 1:4～6 with the molar ratio of ammonia, aminating reaction temperature is 40～80 DEG C, and the response time is 5～60 points
Clock.
Further, described step 4) in, the alkali used by amino nitrile derivative compound VI basic hydrolysis can be hydrogen-oxygen
Change in sodium, potassium hydroxide, barium hydroxide, potassium carbonate, potassium bicarbonate etc. one or more, preferably ammonia
Alkali used by base nitrile derivative compound VI basic hydrolysis is sodium hydroxide or potassium hydroxide, sodium hydroxide or hydrogen
The molar ratio of potassium oxide and amino nitrile derivative compound VI is 1.0～1.20:1, hydrolysis temperature be 60～
100 DEG C, hydrolysis time is 2～4 hours.
Further, described step 5) in, phosphine oxamate two saline solution is diluted to quality after decolouring and remove impurity
Percentage composition is 5%～22%, enters back into bipolar membrane electrodialysis system and carries out bipolar membrane electrodialysis process.
Further, described step 5) in, the caustic solution circulation that alkali room obtains is applied to amino nitrile derivative compound
VI base hydrolysis step.
Further, described step 5) in, bipolar membrane electrodialysis system side and other side are respectively equipped with built-in
The cathode chamber (I) of negative electrode and be provided with the anode chamber (II) of built-in anode, is provided with between cathode chamber and anode chamber
Film pair, a film forms by a spaced Bipolar Membrane (BP) and a cation exchange membrane (C), described
Film is positioned at cathode direction, Bipolar Membrane to Bipolar Membrane with the anode that the relative position of cation exchange membrane is Bipolar Membrane
Negative electrode be positioned at anode direction, be provided with a cation exchange membrane between two Bipolar Membrane, described film is to double
The cathode direction of pole film and anode membrane constitute alkali room (III), anode membrane and Bipolar Membrane anode direction and constitute salt room (IV).
Further, described step 5) in, it is to be passed through phosphine oxamate two saline in salt room that bipolar membrane electrodialysis processes
Solution, is passed through water in alkali room or dilute aqueous slkali, negative electrode and anode are passed through unidirectional current.
Further, described step 5) in, when the pH of salt room is 3.5～5.0, the alkali in extraction alkali room,
Alkaline concentration in dilute alkali room.
The beneficial effects of the present invention is:
1) present invention first uses bipolar membrane electrodialysis technology to prepare phosphine oxamate, then is reacted with ammonia by phosphine oxamate,
Prepare glufosinate-ammonium, it is not necessary to acid adding, it is to avoid substantial amounts of abraum salt waste water produces, and the glufosinate-ammonium purity that obtains
High, yield height, purity reaches more than 98%, and yield reaches more than 97%.
2) the least due to phosphine oxamate dissolubility in water, under 100 grams of hydroecium temperature, the dissolubility of phosphine oxamate is only
There are about 2 grams, therefore, as used bipolar membrane electrodialysis that its salt is fully converted to phosphine oxamate, need it
Saline solution carries out substantial amounts of dilution, in order to obtain phosphine oxamate, needs to concentrate substantial amounts of water, and this necessarily causes and disappears
Consuming substantial amounts of steam, and the phosphine oxamate salt of substantial amounts of dilution, when bipolar membrane electrodialysis, film is higher to power consumption,
The utilization rate of electric current is relatively low, and the processed in units amount of film is substantially reduced；And the present invention is by bipolar membrane electrodialysis terminal
Control at pH=2.5～3.5, phosphine oxamate salt be converted into the mixed solution of phosphine oxamate and phosphine oxamate one salt, it is not necessary to
Being diluted by phosphine oxamate salt, the current utilization rate of film pair can be up to 80%, and the processed in units amount of film is significantly
Increase, reached energy-saving and cost-reducing, reduced the purpose of production cost.
3) when bipolar membrane electrodialysis processes, when the pH of salt room is 3.5～5.0, the alkali in extraction alkali room, add
Alkaline concentration in water dilution alkali room, such operation is conducive to improving current efficiency.
4) aqueous slkali that the present invention obtains in bipolar membrane electrodialysis can recycle, and has saved glufosinate-ammonium
Production cost.
5) present invention uses hydrocyanic acid as cyanating reagent, and the cyanalcohol yield of generation is high, without byproduct sodium chloride,
Without environmental protection pressure.
Accompanying drawing explanation
In order to make the purpose of the present invention, technical scheme and beneficial effect clearer, the present invention provides drawings described below
Illustrate:
Fig. 1 is the process chart of the production method of the glufosinate-ammonium of prior art report；
Fig. 2 is the process chart of the environment friendly clean producing method of the high-purity glufosinate-ammonium of the present invention；
Fig. 3 is the process chart that in the present invention, bipolar membrane electrodialysis processes.
Detailed description of the invention
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described in detail.
Embodiment 1
1) methyl methylphosphinate generates methyl phosphinate derivatives class chemical combination with acrylic aldehyde generation additive reaction
Thing；
In the three neck round bottom flask being dried of nitrogen protection, at 20～30 DEG C, add the methyl phosphonous acid of 1 mole
Methyl ester, the absolute methanol of 300 milliliters, the DMF of 2 grams, drip under 25 DEG C of stirrings continuously
Adding acrylic aldehyde and the mixture of 1.0 moles of acetic anhydride of 1.05 moles, reaction is exothermic reaction, controls whole mistake
Journey is warm at 25 DEG C in keeping, and control time for adding is within 1～3 hour, at 25～30 DEG C after completion of dropwise addition
Lower insulation reaction 2～4 hours, the residual volume of methyl methylphosphinate in gas chromatogram middle control analysis reaction system,
When methyl methylphosphinate residual volume is considered as reacting completely less than 10ppm, then steam under condition of negative pressure
Except a small amount of acrylic aldehyde, obtaining the methanol solution 560 grams of product, yield is 99%, the quality hundred of compound
Mark is 39.63%.
2) by step 1) the methyl phosphinate derivatives quasi-compound that obtains generates methyl Asia phosphine with hydrocyanic acid
Acid esters cyanohydrin compound；
At a temperature of 25～35 DEG C, to step 1) addition compound product that obtains slowly drips 99.5% hydrocyanic acid
29 grams, it is maintained at 6～7 by saturated sodium bicarbonate aqueous solution regulation reaction system pH, dripped whole
Cheng Zhong, temperature is always maintained at less than 40 DEG C, and after dropping, 30 DEG C are incubated 2 hours, use high-efficient liquid phase color
The residual volume of methyl phosphinate derivatives quasi-compound in analysis of spectrum reaction system, when residual volume is less than
10ppm, is considered as reacting completely, obtains the methanol solution 591 grams of product, and yield is 99%.
3) by step 2) the methyl phosphinate cyanohydrin compound that obtains reacts with ammonia, obtains amino nitrile and derive
Compound；
Step 2 is added in autoclave) methanol solution of compound that obtains, it is subsequently adding 5 moles
The ammonia spirit of 50%, is warming up to 80 DEG C, and in still, pressure is 1.0Mpa, reacts 50 minutes, stopped reaction,
Obtain amino nitrile derivative compound solution.
4) by step 3) the amino nitrile derivative compound basic hydrolysis that obtains, obtain phosphine oxamate disodium salt aqueous solution；
In flask with three necks,round bottom, add 40% sodium hydrate aqueous solution of 1.1 moles, sodium hydroxide is water-soluble
Liquid is heated to 60 DEG C, the most slowly by step 3) compound solution that obtains drops to sodium hydrate aqueous solution
In, keep the temperature of reaction system during dropping less than 80 DEG C, to release substantial amounts of ammonia.After dropping,
Be warming up to 100 DEG C immediately and continue hydrolysis 2 hours, then under conditions of negative pressure by ammonia substantially from reaction
Removing in system, the maximum residue limit of ammonia is 50ppm.Except the feed liquid after ammonia proceeds in autoclave, so
The most airtight being heated to 160 DEG C, in still, pressure is 2.0Mpa, keeps 30 minutes, is then cooled to room temperature,
To phosphine oxamate disodium salt aqueous solution, this solution is brown, carries out decolouring through NF membrane, except mechanicalness impurity,
Obtaining flaxen transparent phosphine oxamate disodium salt aqueous solution 710 grams, weight/mass percentage composition is 25%, yield
It is 98%.The phosphine oxamate disodium salt aqueous solution deionized water obtained is diluted to weight/mass percentage composition is 19%.
5) with step 4) the phosphine oxamate disodium salt aqueous solution that obtains as raw material, enter bipolar membrane electrodialysis system
Carrying out bipolar membrane electrodialysis process, salt room controls pH=2.5～3.5 and obtains the mixed of phosphine oxamate and phosphine oxamate one sodium salt
Closing solution, alkali room obtains sodium hydroxide solution；
Bipolar membrane electrodialysis system side and other side are respectively equipped with the cathode chamber (I) of built-in negative electrode and are provided with
The anode chamber (II) of built-in anode, is provided with film pair between cathode chamber and anode chamber, a film is to by spaced
One Bipolar Membrane (BP) and a cation exchange membrane (C) composition, described film is to Bipolar Membrane and cation exchange membrane
Relative position be that the anode of Bipolar Membrane is positioned at cathode direction, the negative electrode of Bipolar Membrane is positioned at anode direction, two
Being provided with a cation exchange membrane between Bipolar Membrane, cathode direction and the anode membrane of Bipolar Membrane are constituted by described film
Alkali room (III), anode membrane and Bipolar Membrane anode direction constitute salt room (IV)；Phosphine oxamate disodium it is passed through in salt room
Saline solution, is passed through the sodium hydroxide solution that mass fraction is 0.1% in alkali room, negative electrode and anode are passed through direct current
Electricity；When the pH of salt room is 3.5～5.0, the sodium hydroxide in extraction alkali room, remaining in dilute alkali room
Remaining naoh concentration is to 0.1%；It is electrodialysis terminal that pH in salt room controls 2.5～3.5, analyzes
Phosphine oxamate-phosphine oxamate one sodium salt in salt room, its yield is 100% (in terms of phosphine oxamate sodium salt)；The hydrogen of alkali room
Sodium oxide, through concentrating, is analyzed wherein phosphine oxamate, is not detected, obtain the sodium hydrate aqueous solution of 45%,
Return to the base hydrolysis step of amino nitrile derivative compound.
6) by step 5) phosphine oxamate-phosphine oxamate one sodium-salt aqueous solution of obtaining is through being concentrated into 25%, the coldest
But to 5 DEG C of crystallizations, sucking filtration obtains phosphine oxamate wet product, drying, obtains the phosphine oxamate of content 98.5%；Crystallization
Mother solution is through analyzing mainly phosphine oxamate one sodium salt, and Recycling Mother Solution to bipolar membrane electrodialysis system continues preparation grass amine
Phosphine, repeats aforesaid operations, and the phosphine oxamate gross mass finally obtained is 171.3 grams, and purity is 98.5%, yield
Being 97% (phosphine oxamate disodium salt meter), current utilization rate is 80%.
7) by step 6) phosphine oxamate that obtains reacts with ammonia, prepares glufosinate-ammonium；
Phosphine oxamate is added in 25% ammonia of 68 grams, be stirred at room temperature 1 hour, the most under negative pressure water steamed
Removing, obtain glufosinate-ammonium crystal, dry and obtain 188.2 grams, purity is 98%, and yield is 99.9%.
Embodiment 2
The step 1 of embodiment 2,2,3 same as in Example 1.
4) by step 3) the amino nitrile derivative compound basic hydrolysis that obtains, obtain phosphine oxamate di-potassium aqueous solution；
In flask with three necks,round bottom, add 40% potassium hydroxide aqueous solution of 1.1 moles, potassium hydroxide is water-soluble
Liquid is heated to 60 DEG C, the most slowly by step 3) compound solution that obtains drops to potassium hydroxide aqueous solution
In, keep the temperature of reaction system during dropping less than 80 DEG C, to release substantial amounts of ammonia.After dropping,
Be warming up to 100 DEG C immediately and continue hydrolysis 2 hours, then under conditions of negative pressure by ammonia substantially from reaction
Removing in system, the maximum residue limit of ammonia is 50ppm.Except the feed liquid after ammonia proceeds in autoclave, so
The most airtight being heated to 160 DEG C, in still, pressure is 2.0Mpa, keeps 30 minutes, is then cooled to room temperature,
To phosphine oxamate di-potassium aqueous solution, this solution is brown, carries out decolouring through NF membrane, except mechanicalness impurity,
Obtaining flaxen transparent phosphine oxamate di-potassium aqueous solution 720 grams, weight/mass percentage composition is 22%, yield
It is 98%.The phosphine oxamate di-potassium aqueous solution deionized water obtained is diluted to weight/mass percentage composition is 19%.
5) with step 4) the phosphine oxamate di-potassium aqueous solution that obtains as raw material, enter bipolar membrane electrodialysis system
Carrying out bipolar membrane electrodialysis process, salt room controls pH=2.5～3.5 and obtains the mixed of phosphine oxamate and phosphine oxamate one potassium salt
Closing solution, alkali room obtains potassium hydroxide solution；
Bipolar membrane electrodialysis system side and other side are respectively equipped with the cathode chamber (I) of built-in negative electrode and are provided with
The anode chamber (II) of built-in anode, is provided with film pair between cathode chamber and anode chamber, a film is to by spaced
One Bipolar Membrane (BP) and a cation exchange membrane (C) composition, described film is to Bipolar Membrane and cation exchange membrane
Relative position be that the anode of Bipolar Membrane is positioned at cathode direction, the negative electrode of Bipolar Membrane is positioned at anode direction, two
Being provided with a cation exchange membrane between Bipolar Membrane, cathode direction and the anode membrane of Bipolar Membrane are constituted by described film
Alkali room (III), anode membrane and Bipolar Membrane anode direction constitute salt room (IV)；Phosphine oxamate dipotassium it is passed through in salt room
Saline solution, is passed through the potassium hydroxide solution that mass fraction is 0.1% in alkali room, negative electrode and anode are passed through direct current
Electricity；When the pH of salt room is 3.5～5.0, the potassium hydroxide in extraction alkali room, remaining in dilute alkali room
Remaining concentration of potassium hydroxide is to 0.1%；It is electrodialysis terminal that pH in salt room controls 2.5～3.5, analyzes
Phosphine oxamate-phosphine oxamate one potassium salt in salt room, its yield is 100% (in terms of phosphine oxamate potassium salt)；The hydrogen of alkali room
Potassium oxide, through concentrating, is analyzed wherein phosphine oxamate, is not detected, obtain the potassium hydroxide aqueous solution of 45%,
Return to the base hydrolysis step of amino nitrile derivative compound.
6) by step 5) phosphine oxamate-phosphine oxamate one potassium salt aqueous solution of obtaining is through being concentrated into 25%, the coldest
But to 5 DEG C of crystallizations, sucking filtration obtains phosphine oxamate wet product, drying, obtains the phosphine oxamate of content 98.5%；Crystallization
Mother solution is through analyzing mainly phosphine oxamate one potassium salt, and Recycling Mother Solution to bipolar membrane electrodialysis system continues preparation grass amine
Phosphine, repeats aforesaid operations, and the phosphine oxamate gross mass finally obtained is 171.4 grams, and purity is 98.5%, yield
Being 97% (phosphine oxamate di-potassium meter), current utilization rate is 80%.
7) by step 6) phosphine oxamate that obtains reacts with ammonia, prepares glufosinate-ammonium；
Phosphine oxamate is added in 25% ammonia of 68 grams, be stirred at room temperature 1 hour, the most under negative pressure water steamed
Removing, obtain glufosinate-ammonium crystal, dry and obtain 188.2 grams, purity is 98%, and yield is 99.9%.
Finally illustrate, preferred embodiment above only in order to technical scheme to be described and unrestricted,
Although the present invention being described in detail by above preferred embodiment, but those skilled in the art
Should be appreciated that and in the form and details it can be made various change, without departing from the present invention
Claims limited range.
Claims (7)
1. the environment friendly clean producing method of a high-purity glufosinate-ammonium, it is characterised in that: include following step
Rapid:
1) methyl phosphinate compound I and acrylic aldehyde generation additive reaction are generated methyl phosphinate to spread out
Biological species compounds Ⅳ；
2) by step 1) to generate methyl sub-for the methyl phosphinate derivatives quasi-compound that obtains IV and cyanide
Phosphonate ester cyanohydrin compound V；
3) by step 2) the methyl phosphinate cyanohydrin compound V that obtains reacts with ammonia, obtains amino nitrile and spread out
Raw compounds VI；
4) by step 3) amino nitrile derivative compound VI basic hydrolysis that obtains, obtain phosphine oxamate disalt water-soluble
Liquid；
5) with step 4) phosphine oxamate two saline solution that obtains as raw material, enter bipolar membrane electrodialysis system
Carrying out bipolar membrane electrodialysis process, salt room controls pH=2.5～3.5 and obtains the mixed of phosphine oxamate and phosphine oxamate one salt
Closing solution, alkali room obtains aqueous slkali；
6) by step 5) mixed solution of the phosphine oxamate that obtains and phosphine oxamate one salt concentrate after crystallisation by cooling,
Obtaining phosphine oxamate and crystalline mother solution, crystalline mother solution is recycled to step 5) enter bipolar membrane electrodialysis system carry out
Bipolar membrane electrodialysis processes；
7) by step 6) phosphine oxamate that obtains reacts with ammonia, prepares glufosinate-ammonium；
Described step 5) in, phosphine oxamate two saline solution is diluted to percent mass after decolouring and remove impurity and contains
Amount is 5%～22%, enters back into bipolar membrane electrodialysis system and carries out bipolar membrane electrodialysis process；
Described step 5) in, bipolar membrane electrodialysis system side and other side are respectively equipped with built-in negative electrode
Cathode chamber (I) and be provided with the anode chamber (II) of built-in anode, is provided with film between cathode chamber and anode chamber
Right, a film forms by a spaced Bipolar Membrane (BP) and a cation exchange membrane (C), described
Film is positioned at cathode direction to Bipolar Membrane with the anode that the relative position of cation exchange membrane is Bipolar Membrane, bipolar
The negative electrode of film is positioned at anode direction, is provided with a cation exchange membrane, described film between two Bipolar Membrane
Cathode direction and anode membrane to Bipolar Membrane constitute alkali room (III), anode membrane and Bipolar Membrane anode direction and constitute salt
Room (IV)；
Described step 5) in, it is to be passed through phosphine oxamate two saline solution in salt room that bipolar membrane electrodialysis processes,
Alkali room is passed through water or dilute aqueous slkali, negative electrode and anode are passed through unidirectional current.
The environment friendly clean producing method of high-purity glufosinate-ammonium the most according to claim 1, its feature exists
In: described step 1) in, methyl phosphinate compound I is methyl methylphosphinate, methyl phosphonous acid
Methyl ester is to carry out in the presence of acetic anhydride, N,N-dimethylformamide and methanol with the additive reaction of acrylic aldehyde
, methyl methylphosphinate is 1:1.0～1.05 with the molar ratio of acrylic aldehyde, and acetic anhydride rubs with acrylic aldehyde
You than be 1:1.0～1.05, the consumption of DMF be methyl methylphosphinate quality 0.1%～
5%, reaction temperature is 0～50 DEG C, and the response time is 2～5 hours.
The environment friendly clean producing method of high-purity glufosinate-ammonium the most according to claim 1, its feature exists
In: described step 2) in, cyanide is hydrocyanic acid, hydrocyanic acid and methyl phosphinate derivatives class chemical combination
The molar ratio of thing IV is 1.0～1.1:1, and pH during cyaniding is 6～7, and the temperature of cyanogenation controls
At 25～40 DEG C, the cyanogenation time is 3～4 hours.
The environment friendly clean producing method of high-purity glufosinate-ammonium the most according to claim 1, its feature exists
In: described step 3) in, ammonia is ammonia or ammonia, methyl phosphinate cyanohydrin compound V and ammonia
Molar ratio is 1:4～6, and aminating reaction temperature is 40～80 DEG C, and the response time is 5～60 minutes.
The environment friendly clean producing method of high-purity glufosinate-ammonium the most according to claim 1, its feature exists
In: described step 4) in, the alkali used by amino nitrile derivative compound VI basic hydrolysis is sodium hydroxide or hydrogen
The molar ratio of potassium oxide, sodium hydroxide or potassium hydroxide and amino nitrile derivative compound VI be 1.0～
1.20:1, hydrolysis temperature is 60～100 DEG C, and hydrolysis time is 2～4 hours.
The environment friendly clean producing method of high-purity glufosinate-ammonium the most according to claim 1, its feature exists
In: described step 5) in, the caustic solution circulation that alkali room obtains is applied to amino nitrile derivative compound VI aqueous alkali
Solve step.
The environment friendly clean producing method of high-purity glufosinate-ammonium the most according to claim 1, its feature exists
In: described step 5) in, when the pH of salt room is 3.5～5.0, the alkali in extraction alkali room, dilute
Alkaline concentration in alkali room.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410553671.0A CN104262391B (en) | 2014-07-08 | 2014-10-16 | A kind of environment friendly clean producing method of high-purity glufosinate-ammonium |
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| CN201410321289.7 | 2014-07-08 | ||
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| CN201410553671.0A CN104262391B (en) | 2014-07-08 | 2014-10-16 | A kind of environment friendly clean producing method of high-purity glufosinate-ammonium |
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| CN201410469398.3A Expired - Fee Related CN104313636B (en) | 2014-07-08 | 2014-09-16 | A kind of environment-protecting clean production technology of high-purity EDTA-2Na |
| CN201410469444.XA Expired - Fee Related CN104262393B (en) | 2014-07-08 | 2014-09-16 | Energy-saving clean production method and device of glyphosate |
| CN201410469672.7A Expired - Fee Related CN104327115B (en) | 2014-07-08 | 2014-09-16 | A kind of energy-saving clean production method of high-purity glufosinate-ammonium |
| CN201410469750.3A Expired - Fee Related CN104262394B (en) | 2014-07-08 | 2014-09-16 | The environment friendly clean producing method of a kind of preparing glyphosate from N-phosphonomethyl aminodiacetic acid and device |
| CN201410553671.0A Expired - Fee Related CN104262391B (en) | 2014-07-08 | 2014-10-16 | A kind of environment friendly clean producing method of high-purity glufosinate-ammonium |
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| CN201410469398.3A Expired - Fee Related CN104313636B (en) | 2014-07-08 | 2014-09-16 | A kind of environment-protecting clean production technology of high-purity EDTA-2Na |
| CN201410469444.XA Expired - Fee Related CN104262393B (en) | 2014-07-08 | 2014-09-16 | Energy-saving clean production method and device of glyphosate |
| CN201410469672.7A Expired - Fee Related CN104327115B (en) | 2014-07-08 | 2014-09-16 | A kind of energy-saving clean production method of high-purity glufosinate-ammonium |
| CN201410469750.3A Expired - Fee Related CN104262394B (en) | 2014-07-08 | 2014-09-16 | The environment friendly clean producing method of a kind of preparing glyphosate from N-phosphonomethyl aminodiacetic acid and device |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104621178B (en) * | 2015-02-10 | 2016-10-12 | 重庆紫光化工股份有限公司 | A kind of glyphosate pesticide active compound and preparation method thereof |
| CN105154911A (en) * | 2015-08-25 | 2015-12-16 | 杭州蓝然环境技术有限公司 | Technology for producing EDTA through bipolar membrane method |
| CN105541903A (en) * | 2015-12-14 | 2016-05-04 | 浙江新安化工集团股份有限公司 | Preparation method of glufosinate-ammonium |
| CN105669742B (en) * | 2016-01-14 | 2018-06-08 | 江苏七洲绿色化工股份有限公司 | A kind of purification process of glufosinate-ammonium |
| CN105541907B (en) * | 2016-01-14 | 2018-05-11 | 江苏七洲绿色化工股份有限公司 | A kind of purification process of glufosinate-ammonium |
| CN105541905B (en) * | 2016-01-14 | 2018-05-01 | 江苏七洲绿色化工股份有限公司 | A kind of purification process of glufosinate-ammonium |
| CN105541906B (en) * | 2016-01-14 | 2018-05-11 | 江苏七洲绿色化工股份有限公司 | A kind of purification process of glufosinate-ammonium |
| CN105541904B (en) * | 2016-01-14 | 2018-11-13 | 江苏七洲绿色化工股份有限公司 | A kind of purification process of glufosinate-ammonium |
| CN106279269A (en) * | 2016-07-28 | 2017-01-04 | 浙江新安化工集团股份有限公司 | A kind of method preparing glufosinate-ammonium potassium salt |
| CN106518698A (en) * | 2016-09-20 | 2017-03-22 | 重庆紫光化工股份有限公司 | Environmental-protection clean production process for reducing ethylenediaminetetraacetic acid by-production inorganic acid sodium |
| CN106496266B (en) * | 2016-09-27 | 2018-08-17 | 江苏七洲绿色化工股份有限公司 | A kind of preparation method of glufosinate-ammonium |
| CN106496265B (en) * | 2016-09-27 | 2018-08-17 | 江苏七洲绿色化工股份有限公司 | A kind of synthetic method of glufosinate-ammonium |
| CN108148091B (en) * | 2016-12-02 | 2020-01-14 | 利尔化学股份有限公司 | Clean preparation method of glufosinate-ammonium |
| CN112358499A (en) * | 2020-11-12 | 2021-02-12 | 江苏春江润田农化有限公司 | Synthesis method of glufosinate-ammonium |
| CN114605470B (en) * | 2022-04-06 | 2023-08-04 | 中国林业科学研究院林产化学工业研究所 | Method for refining and decoloring glufosinate-ammonium stock solution |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127110A (en) * | 2011-01-28 | 2011-07-20 | 杭州天创净水设备有限公司 | Method for separating and purifying glufosinate-ammonium solution |
| CN103374030A (en) * | 2012-04-13 | 2013-10-30 | 浙江新安化工集团股份有限公司 | Method for preparing glufosinate-ammonium and preparation method for intermediate thereof |
| CN103396440A (en) * | 2013-08-23 | 2013-11-20 | 重庆紫光化工股份有限公司 | Preparation method of glufosinate-ammonium |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3859183A (en) * | 1973-11-07 | 1975-01-07 | Monsanto Co | Process for producing n-phosphonomethyl glycine triesters |
| US4566956A (en) * | 1984-12-07 | 1986-01-28 | The Dow Chemical Company | Electrochemical conversion of soluble salts of insoluble acids to their acid form |
| US4832937A (en) * | 1988-09-28 | 1989-05-23 | The Dow Chemical Company | Regeneration of chelated polyvalent metal solutions by controlled potential electrolysis |
| DE10054993A1 (en) * | 1999-11-10 | 2001-05-17 | Basf Ag | Production of N-phosphonomethylglycine, useful as herbicide, comprises electrochemical oxidation of phosphonomethyliminodiacetic acid using anodically-polarized layer formed by deposition |
| CA2602200A1 (en) * | 2005-04-01 | 2006-10-12 | Monsanto Technology Llc | Control of n-(phosphonomethyl) iminodiacetic acid conversion in manufacture of glyphosate |
| CN101195639B (en) * | 2007-08-02 | 2011-11-16 | 莫一平 | Method for processing mother solution of glyphosate |
| CN101591351A (en) * | 2008-05-28 | 2009-12-02 | 北京紫光英力化工技术有限公司 | The novel process of a kind of pmida98 or its salt glyphosate catalytic oxidation preparation and salt thereof |
| CN101298445A (en) * | 2008-06-17 | 2008-11-05 | 徐昌洪 | Method for directly preparing vitamin C with sodium gulonate |
| CN101748425B (en) * | 2008-12-05 | 2014-07-09 | 宜兴方晶科技有限公司 | Preparation method of stannous methanesulfonate |
| CN101525349A (en) * | 2009-04-10 | 2009-09-09 | 四川贝尔实业有限责任公司 | Method for preparing glyphosate by catalyzing and oxidizing N-phosphonomethyl iminodiacetic acid |
| CN101643408A (en) * | 2009-08-31 | 2010-02-10 | 厦门世达膜科技有限公司 | Production method of gulonic acid in production of vitamin C |
| CN102010431B (en) * | 2010-12-02 | 2012-08-01 | 胡建荣 | Ceftezole sodium compound and novel method thereof |
| CN103664665A (en) * | 2013-12-13 | 2014-03-26 | 天津天成制药有限公司 | Solid sodium sarcosine preparation method |
-
2014
- 2014-09-16 CN CN201410469398.3A patent/CN104313636B/en not_active Expired - Fee Related
- 2014-09-16 CN CN201410469444.XA patent/CN104262393B/en not_active Expired - Fee Related
- 2014-09-16 CN CN201410469672.7A patent/CN104327115B/en not_active Expired - Fee Related
- 2014-09-16 CN CN201410469750.3A patent/CN104262394B/en not_active Expired - Fee Related
- 2014-10-16 CN CN201410553671.0A patent/CN104262391B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102127110A (en) * | 2011-01-28 | 2011-07-20 | 杭州天创净水设备有限公司 | Method for separating and purifying glufosinate-ammonium solution |
| CN103374030A (en) * | 2012-04-13 | 2013-10-30 | 浙江新安化工集团股份有限公司 | Method for preparing glufosinate-ammonium and preparation method for intermediate thereof |
| CN103396440A (en) * | 2013-08-23 | 2013-11-20 | 重庆紫光化工股份有限公司 | Preparation method of glufosinate-ammonium |
Non-Patent Citations (1)
| Title |
|---|
| The feasible study on the reclamation of the glyphosate neutralization liquor by bipolar membrane electrodialysis;Xin-xin Wang, et al.;《Desalination》;20120623;第300卷;第58-63页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104262394A (en) | 2015-01-07 |
| CN104262394B (en) | 2016-08-24 |
| CN104262391A (en) | 2015-01-07 |
| CN104313636B (en) | 2016-08-24 |
| CN104313636A (en) | 2015-01-28 |
| CN104262393B (en) | 2017-01-11 |
| CN104327115B (en) | 2016-08-24 |
| CN104262393A (en) | 2015-01-07 |
| CN104327115A (en) | 2015-02-04 |
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